A novel copper（Ⅱ） complex derived from 1,4,7-triazacyclononane[CuL]_2（PF_6）_3×MeCN×H_2 O was synthesized and crystallographically characterized {L = 1,4-bis（2-carbamoylethyl）-7-benzimidazole-2-yl-meth...A novel copper（Ⅱ） complex derived from 1,4,7-triazacyclononane[CuL]_2（PF_6）_3×MeCN×H_2 O was synthesized and crystallographically characterized {L = 1,4-bis（2-carbamoylethyl）-7-benzimidazole-2-yl-methyl-1,4,7-triazacyclononane}. It crystallizes in triclinic, space group P1, with a = 13.2425（13）, b = 14.0807（15）, c = 17.6798（18）, α = 86.296（2）, β = 72.773（2）, γ= 68.905（2）o, V = 2934.5（5）A^3, Z = 2, D_c = 1.611 g/m^3, F（000） = 1456, M_r = 1423.09, m = 0.920 mm^-1. The final R = 0.0671 and wR = 0.1874 for 6501 observed reflections with I 〉 2σ（I）. The structural analysis shows that the complex cation（[CuL]_2^3＋） was formed by two complex cations, namely（[CuL^3]^2＋） and [CuL_（-H）~3]~＋） through a hydrogen bond. In each complex cation, the Cu（Ⅱ） lies in a distorted square pyramidal geometry. The redox behavior was studied by cyclic voltammetry（CV） in aqueous solution which indicates a reversible one electron redox reaction. The result of UV absorption, ethidium bromide（EB） fluorescence spectra indicated that the complex binds to CT-DNA in an intercalative mode. Superoxide dismutase（SOD） activity of the complex was determined by photoreduction of NBT, and the value of IC_（50） is 5.22 μmol·L^-1.展开更多
Dinuclear Cu(Ⅱ) complexes (Cu,LCl4). 2H2O and Cu2L'Cl4 are pre-pared and characterized by X-ray structure analysis. (Cu2I-Cl4). 2H2O, C20 H40N6Cu2Cl4O2, Mr=665. 54, monoclinic, 6 for 188l observed reflections wit...Dinuclear Cu(Ⅱ) complexes (Cu,LCl4). 2H2O and Cu2L'Cl4 are pre-pared and characterized by X-ray structure analysis. (Cu2I-Cl4). 2H2O, C20 H40N6Cu2Cl4O2, Mr=665. 54, monoclinic, 6 for 188l observed reflections with I>3(I). Cu2L'Cl4, C20H36N6Cu2Cl4, M.=629. 41, monoclinic, for 1330 observed reflections with I>3(I). In both complexes the stereo-chemistry about Cu(Ⅱ) is 5-coordinated with two secondary amine N atoms and twoCl- occupying sites at the base of a distorted square pyramid capped by the tertiaryamine N atom. The pair of Cl' attached to the two Cu(Ⅱ) are held in anti configuration.展开更多
Terbium and N,N′,N' tri(3,5 diamino benzenesulfonyl) 1,4,7 triazacyclononane (TDABS Tacn) form a stable chelate having a 1∶1 molar ratio in dilute aqueous solution. The fluorescence property of the chelate ...Terbium and N,N′,N' tri(3,5 diamino benzenesulfonyl) 1,4,7 triazacyclononane (TDABS Tacn) form a stable chelate having a 1∶1 molar ratio in dilute aqueous solution. The fluorescence property of the chelate was studied under the experimental conditions (pH 8.4 in H 3BO 3 KCl NaOH buffer, λ EX =309 nm, λ EM =374 nm). The fluorescence intensity is a linear function of concentration in the range of 5.0×10 -6 to 4.2×10 -4 mol/L for terbium. The relative standard deviation is less than ±2.0%. When tolerable amount of other metal ions were added to the solution of terbium chelate, the fluorescence intensity can be determined without interference. These results suggest that aromatic armed polyazamacrocycle can be used for the terbium determination.展开更多
The polargraphic behavior of Bi(Ⅲ)-NOTP complex has been investigated inaqueous solution. It was found that under the conditions of pH 3.0 and of 0.02 mol/L NH_4Cl, theBi(Ⅲ)-NOTP system gives a sensitive second orde...The polargraphic behavior of Bi(Ⅲ)-NOTP complex has been investigated inaqueous solution. It was found that under the conditions of pH 3.0 and of 0.02 mol/L NH_4Cl, theBi(Ⅲ)-NOTP system gives a sensitive second order derivative wave at -0.340 V(vs SCE), which isproved to be an adsorptive complex wave. The composition of the complex is Bi(Ⅲ):NOTP. Furthermore,the peak current is linear to the concentration of Bi(Ⅲ) in the range from 3.0x10^(-8) to5.0x10^(-6) mol/L. Artificial and practical samples have been detected with high sensitivity andreceptivity.展开更多
The bicyclic cryptand 1,4,7, 10,13,16,21, 24-octaaza-bigcyclo [8, 8,8] hexacosan-3, 8, 12, 17, 20, 25-hex-one (COBH) bearing diaminoethane groups along the eight-atom bridges was synthesized. The structure consists of...The bicyclic cryptand 1,4,7, 10,13,16,21, 24-octaaza-bigcyclo [8, 8,8] hexacosan-3, 8, 12, 17, 20, 25-hex-one (COBH) bearing diaminoethane groups along the eight-atom bridges was synthesized. The structure consists of discrete neutral macrobicyclic units; the two cycles share the two tertiary amine nitrogen atoms, which exhibit an endo-cndo conformation. Three identical branches formed by 1, 2-diaminoethane link the two tertiary amine groups. The protonation reactions of cryptand (COBH) and its complex formation with copper (II) were investigated by potentiometry in water and in a DMSO/water (80:20 in mass ratio) mixture as solvents. The cryptand acts as a his-base through its two N-bridgehead and exhibits a strong cooperativity that favors the first protonation and makes the second one difficult (△pK= 5.0). An inward rotation of the amide groups to form hydrogen bonds accounts for this cooperativity. The interaction of COBH with copper (II) leads to several binuclear complex proton contents.展开更多
Two supramolecular complexes [Zn（tacd）2]（C6H8O4）·6H2O（1） and [Cu（tacd）2]Cl2·4H2O（2） were synthesized and characterized by elemental analysis, IR spectra, TGA and single-crystal X-ray diffraction an...Two supramolecular complexes [Zn（tacd）2]（C6H8O4）·6H2O（1） and [Cu（tacd）2]Cl2·4H2O（2） were synthesized and characterized by elemental analysis, IR spectra, TGA and single-crystal X-ray diffraction analysis. The crystal structure showed that the metal ions in complexes 1 and 2 had similar coordination circumstance. But for the complex 2, it formed a novel two-dimensional supramolecular network with 12-membered rings and four-membered rings via hydrogen bond interaction. The thermal gravimetric analyses indicated that the two complexes had similar steps of weight-loss. On the basis of experiment, the two complexes were calculated by DFT-B3LYP/6-31G（d） in Gaussian 03. The results of calculation are in good agreement with the experiment.展开更多
基金supported by the Natural Science Foundation of Hubei Province(2014CFB410)
文摘A novel copper（Ⅱ） complex derived from 1,4,7-triazacyclononane[CuL]_2（PF_6）_3×MeCN×H_2 O was synthesized and crystallographically characterized {L = 1,4-bis（2-carbamoylethyl）-7-benzimidazole-2-yl-methyl-1,4,7-triazacyclononane}. It crystallizes in triclinic, space group P1, with a = 13.2425（13）, b = 14.0807（15）, c = 17.6798（18）, α = 86.296（2）, β = 72.773（2）, γ= 68.905（2）o, V = 2934.5（5）A^3, Z = 2, D_c = 1.611 g/m^3, F（000） = 1456, M_r = 1423.09, m = 0.920 mm^-1. The final R = 0.0671 and wR = 0.1874 for 6501 observed reflections with I 〉 2σ（I）. The structural analysis shows that the complex cation（[CuL]_2^3＋） was formed by two complex cations, namely（[CuL^3]^2＋） and [CuL_（-H）~3]~＋） through a hydrogen bond. In each complex cation, the Cu（Ⅱ） lies in a distorted square pyramidal geometry. The redox behavior was studied by cyclic voltammetry（CV） in aqueous solution which indicates a reversible one electron redox reaction. The result of UV absorption, ethidium bromide（EB） fluorescence spectra indicated that the complex binds to CT-DNA in an intercalative mode. Superoxide dismutase（SOD） activity of the complex was determined by photoreduction of NBT, and the value of IC_（50） is 5.22 μmol·L^-1.
文摘Dinuclear Cu(Ⅱ) complexes (Cu,LCl4). 2H2O and Cu2L'Cl4 are pre-pared and characterized by X-ray structure analysis. (Cu2I-Cl4). 2H2O, C20 H40N6Cu2Cl4O2, Mr=665. 54, monoclinic, 6 for 188l observed reflections with I>3(I). Cu2L'Cl4, C20H36N6Cu2Cl4, M.=629. 41, monoclinic, for 1330 observed reflections with I>3(I). In both complexes the stereo-chemistry about Cu(Ⅱ) is 5-coordinated with two secondary amine N atoms and twoCl- occupying sites at the base of a distorted square pyramid capped by the tertiaryamine N atom. The pair of Cl' attached to the two Cu(Ⅱ) are held in anti configuration.
文摘Terbium and N,N′,N' tri(3,5 diamino benzenesulfonyl) 1,4,7 triazacyclononane (TDABS Tacn) form a stable chelate having a 1∶1 molar ratio in dilute aqueous solution. The fluorescence property of the chelate was studied under the experimental conditions (pH 8.4 in H 3BO 3 KCl NaOH buffer, λ EX =309 nm, λ EM =374 nm). The fluorescence intensity is a linear function of concentration in the range of 5.0×10 -6 to 4.2×10 -4 mol/L for terbium. The relative standard deviation is less than ±2.0%. When tolerable amount of other metal ions were added to the solution of terbium chelate, the fluorescence intensity can be determined without interference. These results suggest that aromatic armed polyazamacrocycle can be used for the terbium determination.
基金This project is financially supported by the National Natural Science Foundation of China (No.29575207) KJCXGC-01 of Northwest Normal University
文摘The polargraphic behavior of Bi(Ⅲ)-NOTP complex has been investigated inaqueous solution. It was found that under the conditions of pH 3.0 and of 0.02 mol/L NH_4Cl, theBi(Ⅲ)-NOTP system gives a sensitive second order derivative wave at -0.340 V(vs SCE), which isproved to be an adsorptive complex wave. The composition of the complex is Bi(Ⅲ):NOTP. Furthermore,the peak current is linear to the concentration of Bi(Ⅲ) in the range from 3.0x10^(-8) to5.0x10^(-6) mol/L. Artificial and practical samples have been detected with high sensitivity andreceptivity.
基金the National Natural Science Foundation of China (No.29875018) and the Natural Science Foundation of Gansu Province (ZS991-A25-
文摘The bicyclic cryptand 1,4,7, 10,13,16,21, 24-octaaza-bigcyclo [8, 8,8] hexacosan-3, 8, 12, 17, 20, 25-hex-one (COBH) bearing diaminoethane groups along the eight-atom bridges was synthesized. The structure consists of discrete neutral macrobicyclic units; the two cycles share the two tertiary amine nitrogen atoms, which exhibit an endo-cndo conformation. Three identical branches formed by 1, 2-diaminoethane link the two tertiary amine groups. The protonation reactions of cryptand (COBH) and its complex formation with copper (II) were investigated by potentiometry in water and in a DMSO/water (80:20 in mass ratio) mixture as solvents. The cryptand acts as a his-base through its two N-bridgehead and exhibits a strong cooperativity that favors the first protonation and makes the second one difficult (△pK= 5.0). An inward rotation of the amide groups to form hydrogen bonds accounts for this cooperativity. The interaction of COBH with copper (II) leads to several binuclear complex proton contents.
基金Project supported by the National Natural Science Foundation of China （No. 20271041） and S haanxi Natural Science Foundation （No. 2002B04）.Acknowledgments We are grateful for Prof. Wen Zhenyi, who supplied the Gaussian 03 software for us. We also thank Prof. Ng Seik Weng at University of Malaya for the solution of the crystal structure of complex 1.
文摘Two supramolecular complexes [Zn（tacd）2]（C6H8O4）·6H2O（1） and [Cu（tacd）2]Cl2·4H2O（2） were synthesized and characterized by elemental analysis, IR spectra, TGA and single-crystal X-ray diffraction analysis. The crystal structure showed that the metal ions in complexes 1 and 2 had similar coordination circumstance. But for the complex 2, it formed a novel two-dimensional supramolecular network with 12-membered rings and four-membered rings via hydrogen bond interaction. The thermal gravimetric analyses indicated that the two complexes had similar steps of weight-loss. On the basis of experiment, the two complexes were calculated by DFT-B3LYP/6-31G（d） in Gaussian 03. The results of calculation are in good agreement with the experiment.
